Monoazo dyestuffs containing an aminosulfonyl dialkylamino radical



are of low water-solubility and which correspond to the general formula In this formula R represents hydrogen, (lower)alky1, (e.g. methyl, propyl, butyl), fluorine, chlorine or bromine, R represents hydrogen, (lower)alkyl (e.g. methyl, propyl, butyl), (lower) alkoxy (e.g. methoxy, butoxy), chlorine or bromine, R represents alkyl of 1 to 5 carbons, (lower)alkoxy (e.g. rnethoxy, butoXy), (lower)acylamino (e.g. acetylamino, propionylamino), chlorine, bromine or fluorine, and R represents hydrogen, er)all iyl (e.g. methyl, propyl, butyl), chlorine or bromine. Preferably at least one of the symbols R R and R represents hydrogen.

(Lower)alky means alkyl containing 1 to 4, or particularly 1 to 2 carbon atoms. Preferably the radical (lower)alkyl N S O -NH (lowcrhrlkyl is connected to the nucleus in the position 3 or 4.

The process for the production of the new-dyestuffs consists in coupling a diazotized amine of the general formula (lower) alltyl R2 R1 NSO2NH I I (lower) alkyl -NH;

I B4 (II) with a hydroxy benzene of the general formula R (III) preferably at pH values above 7, especially at 7-12, in the manner described in the examples.

The new monoazo dyestuffs of low water-solubility dye from aqueous dispersion synthetic polyarnide fibers such as nylon and Perlon (registered trademark); cellulose l atented oh. 9, i965 ester fibers, e.g. secondary cellulose acetate and triacetate; polyvinyl fibers; acrylic and modified acrylic fibers, especially polyacrylonitrile fibers, polyester fibers, preferably terephthalic acid ester fibers such as Terylene, Dacron, Dacron 64, Kodel and Vycron (registered trademarks) in yellow or orange shades. The dyestuffs can also be applied to the same fibers by padding or printing techniques. They have good building-up properties on these fibers. The dyeings and prints possess very good fastness to light, gas fumes, washing, heat setting, pleating, sublimation, perspiration, Water and sea Water, and are dischargeable. A fairly good reserve of viscose rayon, cotton, and wool is obtained, especially on aftertreatment with a hydrosulfite. The new dyestuffs are also suitable for coloring lacquers, oils, plastics and artifical fibers in the mass. Cellulose acetate and triacetate dyed in the dope with these dyestuffs have high fastness to light, washing, perspiration, gas fumes, cross dyeing, alkaline bleaching, oxalic acid, dry cleaning and peroxide bleaching, and excellent fastness to water, sea Water, soap baths, crocliing, decatizing and pressing.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAIVIPLE 1 21.5 parts of 1-a1nino-4-dimethyla1ninosulfonylan1ino benzene are dissolved cold in a mixture of 109 parts of water and 36 parts of 30% hydrochloric acid and diazotized with a solution of 7 parts of sodium nitrite and 20 parts of Water at The clear diazo solution obtained is added dropwise with vigorous stirring to a solution of 11 parts of 1-hydroxy-4-methyl-benzene, 14 parts of 30% sodium hydroxide solution, 30 parts of sodium carbonate and 206 parts of water at about 5. After a short time coupling is completed and the brown-yellow precipitate is filtered off, washed neutral with water and dried with vacuum at about The crude product so formed is obtained in almost quantitative yield and is sufficiently pure for coloristic purposes. It can easily be obtained in an analytically pure state, however, by re-crystallization from ethyl alcohol. It then melts at dissolves in concentrated sulfuric acid and in organic solvents with a yellow coloration and possesses in dimethylformamide solution an absorption maximum at 400 m a specific extension coefficient 6* of 47.4 and a molar extinction coeiliciente of 15.8 X 10 The new dyestult dyes from aqueous dispersion acetate, triacetate, synthetic polyainide fibers and polyester fibers in yellow shades of high tinctorial strength and excellent fastness to light, washing, perspiration, sea water, gas fumes, sublimation, pleating and cross-dyeing. The dyeings are dischargeable. The dyestuif gives a good reserve of cotton viscose and wool, and the reserve can be improved by a suitable aftertreatrnent, e.g. with hydrosulfite. The outstanding washing fastness of this dyestuft on synthetic poly-amide fibers is especially notable.

Synthetic polyarnide fibers are dyed as follows: 4 parts of the new dyestuff and 6 parts of suhite cellulose waste powder are ground together. 1 part of the preparation obtained is pasted with a little water and made up to 2000 parts with 2 parts of a fatty alcohol suifonate and the necessary amount of water. 198 parts of nylon are entered and the dyebath heated to 1G0 and boiled for 1 hour. The dyed nylon is then removed, rinsed and dried.

Polyester fibers are dyed as follows: 7 parts of the new dyestuff and 4 parts of sodium dinaphthylrnethanedisulfonate, 4 parts of sodium cetyl sulfate and parts of anhythe crude nitro compound obtained is dissolved in 100 drous sodium sulfate are ground in a ball mill for 48 hours parts of ethyl alcohol and reduced in presence of 2 parts to give a fine powder. 1 part of the resulting dyeing prepof Raney nickel catalyst at 50 with 7.5 liters of hydrogen aration is dispersed in a little water and the dispersion (theoretical uptake 7.4 liters). added through a sieve to a dyebath containing 2 parts of 5 After separation of the catalyst the solution is carefully sodium lauryl sulfate in 4000 parts of water. 100 parts of evaporated in vacuum and then cooled to 0. The pre- 21 scoured fabric of Dacron (registered trademark) polycipitated amino compound is filtered oil and dried. It is ester fiber are entered at 40-50, the bath heated slowly analytically pure and melts at 122123. The reduction and dyeing continued for l2 hours at 95l00 in 'presproceeds quantitatively and gives the new amino comence of 20 parts of an emulsion of a chlorinated benzene pound in excellent yield and purity. in water. The yellow dyeing obtained is then rinsed, soaped, rinsed again and dried. It is fast to light, cross- EXAMPLE 2 dyeing, washing, water, :sea water, perspiration, gas fumes, 21.5 parts of l-amino-3-di1nethylarninosulfonylaminosublimation, heat setting and pleating, and is white disbenzene are diazotized as described in Example 1 and are chargeable. coupled with 11 parts of 1-hydroXy-4-methyl-benzene. The same procedure can be used to dye 100 parts of The dyestuif obtained has good properties especially on .Arnel (registered trademark) triacetate fiber in a yellow polyester. shade with similar fastness properties, no addition of car- EXAMFLE 3 rier being necessary. 21 5 I a o q 1 V 1 parts of 1-am1no-3-d1rnethylaminosulfonylammois gaggg g gfi gasf heed m this example 15 new 2O benzene are diazotized as described in Example 1 and are 't z 13.8 parts of 4-nitro-l-aminobenzene are dissolved in 25 couplfid W1 A 15 parts of 1 hydloky 4 chloro hen ene parts of pyridine and at 10, 15.7 parts of dimethylarnino- EXAMPLE 4 sulfonic acid chloride are added dropwise. The reaction mass is stirred for 10 hours at room temperature and then 25 parts of 1'amlilo'g'-fi'lmethylamniosulfionylammo' 2-chloro-benzene are diazotized as described in Example added with vigorous stirring to a mixture of 40 parts of 1 and are coupled with 11 parts of 1-l1ydroXy-4-methyltechnical 30% hydrochloric acid and parts of ICE. The a 4 benecnc. The fastness properties of dyelngs ootamed precipitated product is filtered off and washed neutral. In th crud tat m h t d t with this dyestuif on fiber materials of synthetic polyamrde t a s e 1 e s a an on re'crys (nylon) and secondary cellulose acetate are especially lization rrom ethyl alcohol at 146 30 good fi f g g g fig P m pracucany quanma" In the following table further monoazodyestuffs are re- We yle as l C n cited which can be produced in a manner analogous to that described in Example 1 and which are suitable for (CH)2NSO NH* NO dyeing synthetic polyarnide and other artificial fibers.

Table Position of Shade of Example No. (Lower) (lower)a1kyl R1 R1 R4 s dyeing on alkyl N s 02 N1.I artificial fibers (lower)alky1 I i lL l i IIl i OOPD NI-I-CO-CHa 5 6 What we claim is: 4. The monoazo dyestuif of the formula 1. Monoazo dyestufi of the formula CH3 k (lower) a1 yl R2 R1 OH OZ NH H NSO;,--NH I I k 6 1 5 C 3 NN- (lower) :11 yl 3 2 1 N- N 6 2 R; (I) I IH--COCH wherein 5. The monoazo dyestutf of the formula R 1s a member selected from the group consisting of hydrogen, (1ower)alkyl, fluorine, chlorine and OH OH bromine, R is a member selected firom the group consisting of hydrogen, (lower)alkyl, (lower)alkoxy, chlorine and 011 bromine, R is a member selected from the group consisting of alkyl of 1 to 5 carbons, (lower)alkoxy, (lower)acyl- CH1 amino, chlorine, bromine and fluorine, and 6. The monoazo dyestufif of the formula R is a member selected from the group consisting of OH hydrogen, (lower) alkyl, chlorine and bromine. 0 2. The monoazo dyestulr of the formula CH3 Cg N-SO -ITTH OH CH3 QN=N (12m 7. The monoazo dyestufi of the formula or 0H CH s: l 3. The m-onoazo dyestutf of the formula /N-SO NH-N=N l CH3 I References (Cited in the file of this patent UNITED STATES PATENTS 01 2,909,515 Ruckstuhl et a1 Oct. 20, 1959 

1. MONOAZO DYESTUFF OF THE FORMULA 